WO1996011177A1

WO1996011177A1 - Fats

Info

Publication number: WO1996011177A1
Application number: PCT/DE1995/001356
Authority: WO
Inventors: Karl Schmid; Michael Neuss; Michael Nitsche
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-10-10
Filing date: 1995-10-02
Publication date: 1996-04-18
Also published as: DE4436066A1; EP0785918A1

Abstract

The invention concerns novel fats of formula (I), in which R1 stands for a linear or branched alkyl group with eight carbon atoms, provided that the portion of free octanol is less than 5 wt %. The octylpropylene-glycolethers and the sulphates, ethoxylates and ether sulphates derived therefrom are distinguished by improved properties on application.

Description

Fatty substances

Field of the Invention

The invention relates to new fatty substances, a process for the production of the fatty substances by propoxylation of octanol and then removal of free fatty alcohol, processes for the production of surface-active derivatives of these fatty substances and the use of the fatty substances and their derivatives for the production of surface-active agents.

State of the art

Modern washing, rinsing and cleaning agents are subject to ever increasing demands. In addition to special ecotoxicological compatibility, there is a special need for ever better performance. This includes, for example, the reliable avoidance of turbidity or the formation of crystals with a long storage time and low temperatures. Another point, which applies in particular to powder and extrudate detergents, is the improvement in the dissolution rate and thus the detergent capacity in the washing machine. In the field of liquid detergents, products are desired which contain as little water as possible 96/11177 " ² " PCI7DE95 / 01356

contained and are still low viscosity. The development of ever new surfactants is not a solution to this problem. Instead, the skilled worker will try to use synergies between known surfactants by intelligent mixing or to optimize existing products and their manufacturing processes.

DE-Cl 4243643 (Henkel), for example, discloses new mixed ether types of the formula C3_ιo + ( ^po ) l 2-1 7+ (EO) 7_9-butyl ether, which are distinguished from very similar known types by an improved wetting action.

In DE-Al 4237178 (Henkel) it is proposed that the cold behavior of preliminary products for the production of liquid cleaning agents by the addition of nonionic surfactants of the formula ^c 6-10 ⁺ ( ^po ) θ, 5-3 ⁺ ( ^EO ) 4- 10 ^and 12-20 ^(EO) 4-10 ^to achieve.

Finally, WO 94/11487 (Unilever) discloses the use of undecyl alcohol to improve the performance of powdered detergents containing alkyl sulfate.

In view of the problems described when using anionic and nonionic surfactants, these writings at best only offer partial solutions. As before, there is a need for a teaching with the help of which both the problem of low-temperature stability in the case of nonionic surfactants, the problem of the tendency to crystallize alkyl ether sulfates, the problem of unsatisfactory dermatological compatibility of concentrated alkyl sulfate pastes and, at the same time, the problem of insufficient water solubility of detergent powders or extrudates containing alkyl sulfate. The complex object of the invention was to provide a solution to the multitude of problems mentioned.

Description of the invention

The invention relates to fatty substances of the formula (I)

CH ₃

I

in which R ^{1 represents} a linear or branched alkyl radical having 8 carbon atoms, with the hate that the proportion of free octanol is less than 5, preferably less than 1% by weight.

Surprisingly, it was found that the fatty substances according to the invention have advantageous cold behavior. When the octylpropylene glycol ethers are mixed with other anionic and / or nonionic surfactants, a lower viscosity (liquid products) and an increased dissolution rate and detergency (solid products) are observed; In addition, an improvement in the dermatological properties can be determined, which makes it possible to produce highly concentrated, high-performance products which are nevertheless classified as low irritation.

The invention includes the knowledge that these surprising properties relate both to the chosen chemical 96/11177 " ⁴ " PCIYDE95 / 01356

Composition as well as the distillative aftertreatment. Thus, products with a longer alkyl chain and / or a higher degree of propoxylation, despite post-treatment, show just as little an improved cold stability as octylpropylene glycol ether, in the production of which the free octanol was not removed after the propoxylation.

The inventive idea also includes the knowledge that the improved application properties are not limited to octylpropylene glycol ethers, but are also retained in the typical secondary products such as sulfates, ethoxylates and ether sulfates. Octylpropylene glycol ethers are also interesting chemical intermediates.

The invention further relates to a process for the preparation of fatty substances of the formula (I),

CH3

I

in which R ^{1 represents} a linear or branched alkyl radical having 8 carbon atoms, which is characterized in that octanol is etherified with propylene oxide in a manner known per se and then the proportion of unreacted alcohol is distilled to a value of less than 5 , preferably less than 1% by weight. The octylpropylene glycol ethers ("octanol + IPO") are prepared in a manner known per se, preferably by reacting 1 mol of 2-ethylhexanol and in particular n-octanol with 1 mol of propylene oxide in the presence of alkaline catalysts (for example sodium methylate) at 120 to 180 ° C in a pressure vessel under autogenous pressure. Instead of the preferred n-octanol, it is also possible to use technical octyl alcohol, for example as a preliminary step in the fractionation of coconut fatty alcohol.

Fatty alcohol sulfates

The invention further relates to a process for the preparation of fatty substances of the formula (II),

CH ₃

I.

R ¹ 0-CH2CHO-Sθ3X (II)

in which R ^{1 is} a linear or branched alkyl radical having 8 carbon atoms and X is an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, characterized in that

a) etherification of octanol with propylene oxide in a manner known per se, b) the fraction of non-breached alcohol is reduced by distillation to a value of less than 5% by weight, c) sulfation of the octylpropylene glycol ether in a manner known per se and finally d) neutralized with bases.

The sulfation of the octylpropylene glycol ethers can take place in the manner known for fatty acid lower alkyl esters [J. Falbe (ed.), "Surfactants in consumer products", Springer Verlag, Berlin-Heidelberg, 1987, p. 61], with reactors working according to the falling film principle , are preferred. Chlorosulfonic acid and in particular gaseous sulfur trioxide are suitable as sulfonating agents. The latter is usually diluted with an inert gas, preferably air or nitrogen, and used in the form of a gas mixture which contains the sulfonating agent in a concentration of 1 to 8, in particular 2 to 5,% by volume.

The molar ratio of ether to sulfating agent can be 1: 0.9 to 1: 1.3 and preferably 1: 0.95 to 1: 1.05. The sulfation is usually carried out at temperatures from 20 to 50 ° C. With regard to the viscosity of the starting materials on the one hand and the color quality of the resulting sulfation products on the other hand, it has proven to be optimal to carry out the reaction in a temperature range from 25 to 35 ° C.

The acidic sulfonation products obtained in the sulfation are stirred into aqueous bases, neutralized and adjusted to a pH of 6.5 to 8.5. As bases for the neutralization come alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C2_4 * -alkanolamines, for example mono -, di- and triethanolamine as well primary, secondary or tertiary C1-.4- alkylanu.ne as well as glucamines. The neutralization bases are preferably used in the form of 5 to 55% by weight aqueous solutions, 5 to 25% by weight aqueous sodium hydroxide solutions being preferred.

After neutralization, the sulfation products can be bleached in a manner known per se by adding hydrogen peroxide or sodium hypochlorite solution. Based on the solids content in the solution of the sulfation products, 0.2 to 2% by weight of hydrogen peroxide, calculated as a 100% substance, or corresponding amounts of sodium hypochlorite are used. The pH of the solutions can be adjusted using suitable buffering agents, e.g. B. be kept constant with sodium phosphate or citric acid. To stabilize against bacterial contamination, a preservation is also recommended, e.g. B. with formaldehyde solution, p-hydroxybenzoate, sorbic acid or other known preservatives.

Fatty alcohol ethoxylates

The invention further relates to a process for the preparation of fatty substances of the formula (III),

CH3

I.

R ¹ 0-CH2CHO- (CH2CH2θ) _n H (III) in which R ^{1 stands} for a linear or branched alkyl radical having 8 carbon atoms and n for numbers from 1 to 10, which is characterized in that

a) etherifying octanol in a manner known per se with b) propylene oxide, b) if appropriate, reducing the proportion of unreacted alcohol by distillation to a value of less than 5% by weight and c) octylpropylene glycol ether in a manner known per se with an average of 1 to 10 mol Converts ethylene oxide.

The ethoxylation of the octylpropylene glycol ethers can be carried out in the presence of acidic, but preferably alkaline, catalysts such as sodium methylate, potassium hydroxide and the like. If products with a narrow homolog distribution are desired, the use of stontium or barium salts and in particular of calcined hydrotalcites or those hydrophobicized with fatty acids is appropriate. The reaction is usually carried out at temperatures in the range from 120 to 150 and preferably 140 to 160 ° C. and an autogenous pressure in the range from 1 to 5 bar. For the neutralization of basic catalysts, phosphoric acid or lactic acid is generally added to the products.

In this case, an enrichment of the proportion of free, non-propoxylated octanol before the ethoxylation is only necessary if 1 mol of octanol + IPO is to be reacted with less than 7 mol of ethylene oxide. In all other cases, that is to say with higher degrees of ethoxylation, the undesired proportion of free octanol is eliminated by the subsequent reaction Ethylene oxide lowered to below the required limit. This restriction also applies if the ethoxylates are subsequently to be sulfated.

Fatty alcohol ether sulfates

The invention further relates to a process for the production of fatty substances of the formula (TV),

CH ₃

IR ¹ 0-CH2CHO- (CH2CH2θ) _n Sθ3X (IV)

in which R stands for a linear or branched alkyl radical with 8 carbon atoms, n for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, which is characterized in that

a) etherifying octanol with propylene oxide in a manner known per se, b) if appropriate, the amount of unreacted alcohol is reduced by distillation to a value of less than 5% by weight, c) the octylpropylene glycol ether in a manner known per se with an average of 1 to 10 moles of ethylene oxide are reacted, d) the resulting octylpropylene glycol (poly) ethylene glycol ether is sulfated in a manner known per se and finally e) neutralized with bases. The ether sulfates are prepared analogously to the teaching in Chapter "fatty alcohol sulfates and ^H fatty alcohol ethoxylates ^H.

Industrial applicability

After free octanol has been separated off, octylpropylene glycol ethers have a particularly advantageous low-temperature behavior. They enable the production of low-viscosity liquid detergent concentrates and improve the dissolution rate of powder detergents containing alkyl sulfate. Derivatives of these ethers, in particular sulfates, ethoxylates and ether sulfates, which are collectively subsumed under the term "fatty substances", have interesting surface-active properties, such as, for example, a reduced tendency to crystallize or improved dermatological compatibility, on their own, but especially when mixed with other surfactants.

Another object of the invention finally relates to the use of the fatty substances mentioned for the production of surface-active agents such as, for example, powder detergents, liquid detergents, hand dishwashing detergents, hand washing pastes, all-purpose cleaners, agents for machine bottle cleaning and agents for degreasing metal surfaces.

In preferred embodiments of the invention, the octyl propylene glycol ethers and their sulfates, ethoxylates and / or ether sulfates with anionic surfactants of the fatty alcohol sulfate type (“alkyl sulfates”) and / or fatty alcohol ether sulfates (“ether sulfates”) and nonionic surfactants of the type the fatty alcohol polyglycol ether, mixed ether and alkyl oligoglucoside are mixed. The mixtures can be prepared by known processes from the prior art. If an octylpropylene glycol sulfate or ether sulfate is mixed with another fatty alcohol sulfate or ether sulfate, cosulfation of the starting materials is appropriate.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

96/11177 ^{"12 ■} PCIYDE95 / 01356

Examples

I. Manufacturing examples

Example St.

a) 256 g (2 mol) of n-octanol were placed in a 500 ml steel autoclave and mixed with 4 g of sodium methylate - corresponding to 1% by weight, based on the end product - in the form of a 30% by weight solution in Methanol added. The reactor was closed, rinsed three times alternately with N2 and evacuated. The reaction mixture was then heated to 140 ° C. and 116 g (2 mol) of propylene oxide were injected in portions, the pressure not exceeding 1.5 bar. After the addition had ended, the mixture was stirred for a further 30 min, cooled, let down and the crude ether was adjusted to a pH of 7.5 with lactic acid. The yield was 370 g and was practically quantitative.

b) The crude octylpropylene glycol ether was transferred to a distillation apparatus and unreacted octanol was distilled off at a bottom temperature of about 90 ° C. and a reduced pressure of about 20 mbar. 20 g of octanol were recovered. The distillation residue had a residual octanol content of 0.9% by weight. Example H2

186 g (1 mol) of octylpropylene glycol ether according to Example Hlb) were placed in a 1-1-sulphonation reactor with jacket cooling and reacted at 84 ° C. with 84 g (1.05 mol) of gaseous sulfur trioxide. The sulfur trioxide was driven off from a corresponding amount of 65% oleum by heating, diluted to a concentration of 3% by volume and introduced into the starting product within 25 min. After sulfation, the acidic reaction mixture was stirred in portions into aqueous 25% by weight sodium hydroxide solution and neutralized. The characteristics are summarized in Table 1:

Table 1 Octylpropylene glycol sulfate sodium salt

Anionic surfactant content 27% by weight unsulfated 3% by weight sodium sulfate 1% by weight water 69% by weight

Velcro color 69

The anionic surfactant content (WAS) and the unsulfonated proportions (US) were determined according to the DGF standard methods, Stuttgart 1950-1984, H-III-10 and G-II-6b. The Klett color number was determined after 30 minutes of bleaching with 1% by weight of a 35% by weight aqueous hydrogen peroxide solution. The measurement was carried out at a concentration of 5% by weight of anion surfactant, pH ■ 7 and using a 1 cm round cuvette and a blue filter (400 to 465 nm).

Example H3

Analogously to Example Hlb), 186 g (1 mol) of purified octyl propylene glycol ether were placed in an autoclave with 2.7 g of sodium methylate and 88 g (2 mol) of ethylene oxide were reacted. The octylpropylene glycol-2EO adduct was obtained as a colorless liquid in virtually quantitative yield.

Example H4

130 g (1 mol) of n-ocanol were placed in a 500 ml steel autoclave, and 2.5 g of a 30% by weight solution of sodium methylate in methanol were added. The reactor was closed and flushed three times alternately with nitrogen and evacuated. The reaction mixture was then heated to 140 ° C. and 58.4 g (1 mol) of propylene oxide were injected in portions, the pressure not increasing above 1.5 bar. After the end of the addition, stirring was continued for 30 minutes and 394 g (9 mol) of ethylene oxide were added in the same manner. After a further stirring time of again 30 minutes, the reactor was cooled, the pressure was released and the basic catalyst was neutralized by adding lactic acid. The octyl + lPO + 9EO adduct was obtained in a practically quantitative yield. Example H5

Analogously to Example H2), 274 g (1 mol) of octylpropylene glycol 2E0 adduct from Example H3) were sulfated with 84 g of sulfur trioxide and then neutralized with sodium hydroxide solution. The characteristics are summarized in Table 2:

Table 2 octyl propylene glycol sulfate 2E0 sodium salt

Anionic surfactant content 31% by weight unsulfated 4% by weight sodium sulfate 1% by weight water 64% by weight

Velcro color 55

II. Application studies

The following tests were carried out to investigate the application properties of the fatty substances according to the invention:

(a) Determination of the cold cloud point of various nonionic surfactants (Table 3);

(b) determination of the viscosity of liquid detergent concentrates (Table 4); (c) Dissolution rate of powder detergents. For this purpose, 10 g of different formulations containing alkyl sulfate were dissolved or dispersed in 100 ml of water (30 ° C., 16 ° d). After 30, 120 and 360 s, the solutions or dispersions were filtered off, the residue was dried and weighed (Table 5).

Table 3 Cold Cloud Point (KTP)

Example nonionic surfactant distills KTP

° c

1 octanol + IPO yes 7

VI octanol + IPO no 10

V2 octanol + 2PO yes 12

V3 octanol + 2PO no 13

V4 Decanol + IPO yes 14

V5 decanol + IPO no 16

V6 decanol + 2PO yes 16

V7 Undecanoll) - 17th

V8 Undecanol- ^) - 17th

1) Technical undecyl alcohol Lial ( ^R ) 111 50% linear, 50% multi-branched

2) Technical undecyl alcohol Dobanol ( ^R ) 1 (Shell) 30% branched, 70% linear Table 4 Viscosity of liquid detergents (data as% by weight)

Component 2 3 V9 V10

Octanol + IPO (dest) + 9E0 14 0 0 0

Octanol + IPO (non-dest) + 9E0 0 14 0 0

Coconut fatty alcohol + 7E0 6 6 15 20

Ether sulfate ³ ) 6 6 6 6

Soap ⁴ ) 10 10 10 10

APG ⁵ ) 13 13 13 13

Propylene glycol 8 8 8 8

Water 43 43 48 43

Höppler viscosity 250 330 20000 nm

20 ° C [mPas]

3) Texapon ( ^R ) N70

4) Cg / 13 coconut fatty acid potassium salt

5) Glucopon ( ^R ) 600 UP nm = not measurable, solid paste

Table 5 Dissolution rate of powder detergents (data as% by weight)

Component 4 5 Vll

Alkyl sulfate ⁶ ) 22 22 22

Octanol + IPO (dest) + 9E0 5 0 0

Octanol + IPO (nondest) + 9E0 0 5 0

Tallow Alcohol 1 + 40EO 0 0 5

Zeolite A 35 35 35

Sodium perborate 16 16 16

Water glass 7 7 7

Sodium sulfate 15 15 15

Residue after 30 s (%) 30 35 50

120 s (%) 20 25 35

360 -s (%) 10 18 17

6) Sulfopon ( ^R ) 1218 W.

III. Recipe examples

Example Rl

70% by weight Ci2 / 14 ^-K ° cos fatty alcohol + 2EO sulfate sodium salt

(Texapon ( ^R ) N70, Henkel KGaA, Duesseldorf / FRG) 30% by weight n-octanol + lPO / 2EO sulfate sodium salt

Compared to a pure Texapon ( ^R ) 70, a 40% improvement in cold stability is achieved.

Example R2

70% by weight Ci2 / 14 ^_Kolcosf e ^t ' ^, alcohol + 2EO sulfate sodium salt

(Texapon ( ^R ) N70, Henkel KGaA, Duesseldorf / FRG) 30% by weight n-octanol + lPO sulfate sodium salt

The surfactant compound can be classified as "low irritation" and has a 25% improvement in crystallization inhibition compared to pure Texapon ( ^R ) N70. The compound is suitable for the production of hand dishwashing detergents.

Examples R3 "" ^ W

70 wt .-% Ci6 / 18 ^"Ta lgalkoholsulfat sodium salt

(Sulfopon ( ^R ) T55, Henkel KGaA, Duesseldorf / FRG) 30% by weight n-octanol + IPO sulfate sodium salt

respectively. 14 wt .-% Ci2 / 14- ^{KoJcosa lkylsulfat} sodium salt 56 wt .-% Ci5 / ιg-tallow alcohol sulfate sodium salt 30 wt .-% n-octanol + lPO sulfate sodium salt

Compared to pure sulfone ( ^R ) T55, the dissolution rate in cold water (20 ° C) is improved by 35% and 25%, respectively. The compounds are suitable, for example, for producing hand washing pastes

Example R5

90% by weight Ci2 / 18 ~ ^Ko ^ ^os / ^τ algalkyl sulfate-sodium salt mixture (sulfopone ( ^R ) 1218 W, Henkel KGaA, Düsseldorf / FRG) 10% by weight n-octanol + IPO

The surfactant compound can be granulated or extruded together with 20% by weight of zeolite A, based on the total mixture, to give a dry powder which has a 25% better dissolution than pure sulfopon ( ^R ) 1218 W / zeolite powder. speed in cold water (20 ° C) and has a 10% improved washing performance. In addition, the powder is significantly drier.

Example R6

16% by weight lauryl sulfate sodium salt

(Texapon ( ^R ) NSO, Henkel KGaA, Duesseldorf) 13% by weight C8 / i6 alkyl polyglucoside

(Glucopon ( ^R ) 600 UP, Henkel KGaA, Düsseldorf) 12% by weight Ci2 / 18 ~ ^co- fat alcohol + 7EO

(Lorol ( ^R ) T7, Henkel KGaA, Düsseldorf) 8% by weight n-octanol + lPO / 8EO 8% by weight Ci2 / i & coconut fatty acid 5% by weight potassium hydroxide 8% by weight ethanol 30% by weight % deionized water

The surfactant compound has a very low viscosity (according to Brookfield, RTV viscometer, 20 ° C, spindle 1, 10 rpm) of approx. 300 Pas and can be used as a liquid detergent. On the other hand, if the n-octyl-lPO / 8EO adduct is replaced by Lorol ( ^R ) T7, a cut-resistant gel is obtained.

Example R7

80% by weight Ci2 / 18 ~ ^{coconut oil alcohol + lθEO} '" ^Dut y ^lθtnβr

(Dehyρon ( ^R ) LT 104, Henkel KGaA, Düsseldorf)

20% by weight n-octanol + 1PO / 6EO

The surfactant compound is suitable as a low-foaming wetting agent for the spray cleaning of body panels.

Claims

Patent Proverbs

1. fatty substances of the formula (I),

CH3

I

in which R * represents a linear or branched alkyl radical having 8 carbon atoms, with the proviso that the proportion of free octanol is less than 5% by weight.

2. Process for the preparation of fatty substances of the formula (I),

CH3

I.

R ¹ 0-CH2CH0H (I)

in which R * ^{1 represents} a linear or branched alkyl radical having 8 carbon atoms, characterized in that octanol is etherified with propylene oxide in a manner known per se and then the proportion of unreacted alcohol is distilled to a value of less than 5% by weight. -% depleted.

3. Process for the preparation of fatty substances of the formula (II),

CH ₃

IR ¹ 0-CH ₂ CHO-Sθ3X (II)

in which R ^{1 is} a linear or branched alkyl radical having 8 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, characterized in that

a) etherifying octanol in a manner known per se with propylene oxide, b) depleting the proportion of unreacted alcohol by distillation to a value of less than 5% by weight, c) sulfating the octylpropylene glycol ether in a manner known per se and finally d) neutralizing with bases.

4. Process for the preparation of fatty substances of the formula (HI),

CH ₃

I.

R ¹ 0-CH2CHO- (CH2CH2θ) _n H (III)

in which R ^{1 is} a linear or branched alkyl radical having 8 carbon atoms and n is a number from 1 to 10, characterized in that a) etherifying octanol with propylene oxide in a manner known per se, b) if appropriate, the amount of unreacted alcohol is reduced by distillation to a value of less than 5% by weight and c) the octylpropylene glycol ether in a manner known per se with an average of 1 to 10 mol Converts ethylene oxide.

5. Process for the preparation of fatty substances of the formula (IV),

CH3

I.

R ¹ 0-CH2CHO- (CH2CH2θ) nSθ3X (IV)

in which R ^{1 is} a linear or branched alkyl radical having 8 carbon atoms, n is a number from 1 to 10 and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, characterized in that

a) etherifying octanol in a manner known per se with propylene oxide, b) if appropriate, the amount of unreacted alcohol is reduced by distillation to a value of less than 5% by weight, c) the octylpropylene glycol ether in a manner known per se with an average of 1 to 10 mol Converts ethylene oxide. d) the resulting octylpropylene glycol (poly) ethylene glycol ether sulfated in a manner known per se and finally e) neutralized with bases.

6. Use of fatty substances obtainable by the process according to claims 2 to 5 for the manufacture of powder detergents, liquid detergents, hand dishwashing detergents, hand wash pastes, all-purpose cleaners, agents for machine bottle cleaning and agents for degreasing metal surfaces.